Nutrient concentration, loads and retention in a semiarid micro-estuary: The relative contribution of baseflow and flood events.

Estuaries are a significant source of nutrients to the marine environment. The magnitude of this source is a function of nutrients load reaching the estuary and removal (attenuation) within estuaries. Most estuarine research is conducted in large estuaries, which do not reflect the processes in small estuaries in urban and semi-arid regions where flood water is a substantial portion of the annual discharge and the estuarine baseflow is often low and dominated by wastewater. To improve the understanding of nutrient attenuation and load into the Mediterranean, we conducted high-resolution nutrient sampling in the eutrophic Alexander micro-estuary as a test case. We sampled once per month during baseflows (years 2014-2019) and hourly during floods (years 2016-2018). The concentrations of inorganic nutrients (phosphorous (P) and nitrogen (N)) were extremely high during baseflows. Dissolved ammonium and particulate P were the only nutrients that were in the estuary (by 55 % and 30 %, respectively). Floods were rare, occurring ~4 % of the time, but contributed 62 % of the annual water discharge of the Alexander micro-estuary (14.7 ± 3.8 106 m3 y-1). The concentration of all dissolved nutrients decreased during floods but was higher than expected (DIN 584 ± 50 µmol L-1, phosphate 21 ± 2 µmol L-1), accounting for 42 % and 55 % of the overall annual DIN (123.5 ± 44.9-ton yr-1) and P (6.7 ± 1.9 ton yr-1) loads to sea, respectively. The N:P ratios were 16 and 34 during baseflow and flood events, respectively. Previously, nutrient loads were calculated by multiplying baseflow-measured concentrations by the total water volume of baseflow and floods. Our calculations, based on high-resolution sampling, revealed lower annual loads of P and N to the sea that were 56 % and 89 % of previous estimates, which is a considerable difference in an oligotrophic system such as the eastern Mediterranean.

Wastewater dissolved organic matter: characteristics and sorptive capabilities.

An evaluation of the mobility of organic pollutants with wastewater dissolved organic matter (DOM) is essential to better understanding their fate and toxicity to the environment. In this study, DOM from two wastewater treatment plants (in Lachish and Netanya, Israel) were fractionated to hydrophobic-acid (HoA) and hydrophobic-neutral (HoN) fractions. The fractions were characterised and their sorptive capabilities for s-triazine herbicides and polycyclic aromatic hydrocarbons (PAHs) were studied. For all sorbates, binding to the HoN fractions was much higher than to HoA fractions. The high binding coefficients obtained for the studied triazines by the HoN fractions suggested that their sorption is governed by hydrophobic-like interactions rather than H-bonding. The binding coefficients of PAHs measured for the HoN fractions were within the range reported for humic acids and much higher than for the HoA fraction, suggesting that the HoN fraction plays an important role in the overall sorption of these compounds by DOM. Higher sorption coefficients were measured for the Netanya DOM sample containing a higher level of hydrophobic fractions (HoA + HoN) than the Lachish DOM, suggesting that the sorption of hydrophobic organic compounds by DOM is governed by the relative content of these structural substances.

New approach for the removal of metal ions from water: adsorption onto aquatic plants and microwave reaction for the fabrication of nanometals.

We adsorb heavy metal ions such as Ag(+), Pb(2+), and Ru(3+) onto an aquatic plant and convert the adsorbed ions to the corresponding nanometallic particles by the polyol reaction carried out in a microwave oven.

Characterization of organic matter in pristine and contaminated coastal marine sediments using solid-state 13C NMR, pyrolytic and thermochemolytic methods: a case study in the San Diego harbor area.

Chemical composition of coastal marine sedimentary organic matter (SDOM) is a function of natural and anthropogenic inputs to the system. In this study a combination of analytical techniques: 13C nuclear magnetic resonance (NMR), pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and tetramethylammonium hydroxide thermochemolysis-gas chromatography/mass spectrometry (TMAH thermochemolysis-GC/MS) were used to study the contribution of hydrophobic organic contaminants and terrestrial OM to the SDOM. Sediments were collected from two sites in the San Diego Bay: Paleta Creek, which is contaminated, and Coronado Cayes, which is relatively pristine. Concentrations of polycyclic aromatic hydrocarbons (PAHs) at both sites, as determined by ultrasonically assisted lipid extraction are found to be higher in the surface layer, to generally decrease with depth, and to be present at about two orders of magnitude higher concentration at the contaminated site as compared to the pristine site. The sediment samples were partially deashed with HF/HCI treatment before further analysis. 13C-NMR spectra of the Paleta Creek samples show a higher aromatic carbon content and a distinct phenolic carbon peak. This suggests a large input from terrestrial carbon (lignin). Data from both Py-GC/MS and TMAH thermochemolysis-GC/MS support this and indicate the presence of lignin-derived residues, primarily of the guaiacyl type at the contaminated site. In contrast, SDOM at the Coronado Cayes site exhibits less terrestrial input. In general, the SDOM resembles soil OM rather than typical marine SDOM. Chemical analyses of the lipid-extracted, partially deashed sediments, does not reveal the presence of any PAHs.

Oxidative biodegradation of phosphorothiolates by fungal laccase.

Organophosphorus (OP) insecticides and nerve agents that contain P-S bond are relatively more resistant to enzymatic hydrolysis. Purified phenol oxidase (laccase) from the white rot fungus Pleurotus ostreatus (Po) together with the mediator 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonate) (ABTS) displayed complete and rapid oxidative degradation of the nerve agents VX and Russian VX (RVX) and the insecticide analog diisopropyl-Amiton with specific activity: k(sp) = 2200, 667 and 1833 nmol min(-1) mg(-1), respectively (pH 7.4, 37 degrees C). A molar ratio of 1:20 for OP/ABTS and 0.05 M phosphate at pH 7.4 provided the highest degradation rate of VX and RVX. The thermostable laccase purified from the fungus Chaetomium thermophilium (Ct) in the presence of ABTS caused a 52-fold slower degradation of VX with k(sp) = 42 nmol min(-1) mg(-1). The enzymatic biodegradation products were identified by 31P-NMR and GC/MS analysis.

Purification and characterization of laccase from Chaetomium thermophilium and its role in humification.

Chaetomium thermophilium was isolated from composting municipal solid waste during the thermophilic stage of the process. C. thermophilium, a cellulolytic fungus, exhibited laccase activity when it was grown at 45 degreesC both in solid media and in liquid media. Laccase activity reached a peak after 24 h in liquid shake culture. Laccase was purified by ultrafiltration, anion-exchange chromatography, and affinity chromatography. The purified enzyme was identified as a glycoprotein with a molecular mass of 77 kDa and an isoelectric point of 5.1. The laccase was stable for 1 h at 70 degreesC and had half-lives of 24 and 12 h at 40 and 50 degreesC, respectively. The enzyme was stable at pH 5 to 10, and the optimum pH for enzyme activity was 6. The purified laccase efficiently catalyzed a wide range of phenolic substrates but not tyrosine. The highest levels of affinity were the levels of affinity to syringaldazine and hydroxyquinone. The UV-visible light spectrum of the purified laccase had a peak at 604 nm (i.e., Cu type I), and the activity was strongly inhibited by Cu-chelating agents. When the hydrophobic acid fraction (the humic fraction of the water-soluble organic matter obtained from municipal solid waste compost) was added to a reaction assay mixture containing laccase and guaiacol, polymerization took place and a soluble polymer was formed. C. thermophilium laccase, which is produced during the thermophilic stage of composting, can remain active for a long period of time at high temperatures and alkaline pH values, and we suggest that this enzyme is involved in the humification process during composting.